Electronic Supplementary Material (ESI) for RSC Advances.
This journal is © The Royal Society of Chemistry 2015
Conversion of glucose into 5-hydroxymethylfurfural catalyzed by chromium(III)
schiff base complexes and acidic ionic liquids immobilized on mesoporous silica
Yanfang Wang, Zhen Gu, Wentao Liu, Yuan yao, Haijun Wang*, Xiao-Feng Xia, Wei
Li
aSchool
of Chemical and Material Engineering, Jiangnan University, Wuxi 214122, China
Supplementary Information
Ligand Analysis
Figure S1: 1H NMR spectrum of Salen.
NMR (CDC13, 400 MHz): δ ppm 13.23 (s, 2H), 8.38 (s, 2H), 7.35-7.21 (m, 5H),
6.97 (d, 2H, J = 8.3 Hz), 6.88 (td, 2H, J=7.6, 0.9 Hz), 3.96 (s, 4H).
1H
Figure S2: 1H NMR spectrum of Salen-Cl.
1H NMR (CDC1 , 400 MHz): δ ppm 13.13 (s, 2H), 8.31 (s, 2H), 7.31-7.19 (m, 5H),
3
6.91 (d, 2H, J=8.7 Hz), 3.97 (s, 4H).
Figure S3: 1H NMR spectrum of Salen-Br.
1H NMR (CDC1 , 400 MHz): δ ppm 13.16 (s, 2H), 8.31 (s, 2H), 7.44-7.34 (m, 5H),
3
6.87 (d, 2H, J=8.7 Hz), 3.98 (s, 4H).
(a)
Intensity
Transmittance
(b)
(c)
(b)
(c)
(a)
4000
3500
3000
2500
2000
Wavenumbers(cm-1)
1500
1000
500
300
350
400
450
500
Wavelength(nm)
550
600
Figure S4: FT-IR (KBr disc) and UV-Vis spectrum of Salen(a), Salen-Cl(b), SalenBr(c).
Salen(a), FT-IR(KBr, cm-1): 1633, 1606, 1575, 1460, 1416, 1282, 1020, 813, 749.
UV-Vis spectrum in CH2Cl2 (λmax, nm): 317.
Salen-Cl(b), FT-IR(KBr, cm-1): 3441, 1632, 1482, 1274, 1034, 828, 705, 645. UV-Vis
spectrum in CH2Cl2 (λmax, nm): 330.
Salen-Br(c), FT-IR(KBr, cm-1): 3438, 1634, 1474, 1276, 1033, 826, 776, 691. UV-Vis
spectrum in CH2Cl2 (λmax, nm): 332.
(b)
Transmittance
(c)
(a)
(a)
(c)
(b)
4000
3500
3000
2500
2000
1500
1000
500
Wavenumbers(cm-1)
300
350
400
450
500
Wavelength(nm)
550
600
Figure S4: FT-IR (KBr disc) and UV-Vis spectrum of Cr-Salen(a), Cr(Salen-Cl)(b),
Cr(Salen-Br)(c).
Cr(Salen), FT-IR(KBr, cm-1): 3418, 2921, 1623, 1594, 1449, 1311, 1029, 757, 672,
620, 569. UV-Vis spectrum in CH2Cl2 (λmax, nm): 391.
Cr(Salen-Cl), FT-IR(KBr, cm-1): 3402, 2929, 1625, 1602, 1456, 1383, 1304, 1177,
826, 708, 660. UV-Vis spectrum in CH2Cl2 (λmax, nm): 401.
Cr(Salen-Br), FT-IR(KBr, cm-1): 3426, 2921, 1628, 1594, 1457, 1380,1304, 1177,
1033, 825, 687, 649. UV-Vis spectrum in CH2Cl2 (λmax, nm): 402.
4000
3500
3000
2500
2000
1500
1000
500
-1
Wavenumbers(cm )
Figure S5: FT-IR (KBr disc) spectrum of [CPTES-IM-SO3H][HSO4]
FT-IR(KBr, cm-1): 3443, 3154, 3100, 2952, 1565, 1444, 1361, 1275, 1184, 1046, 840,
608.
Trannsmittance(%)
(a)
4000
3500
3000
2500
2000
1500
1000
500
Wavenumber(cm-1)
Figure S6 (a)FT-IR spectra of Cr(Salen)-IM-Cl-MCM-41
FT-IR(KBr, cm-1): 3441, 3155, 2931, 1625, 1545, 1460, 1388, 1192, 1089, 1048, 803,
740, 601, 524.
Trannsmittance(%)
(b)
4000
3500
3000
2500 2000 1500
Wavenumber(cm-1)
1000
500
Figure S6 (b)FT-IR spectra of Cr(Salen-Cl)-IM- HSO4-MCM-41.
FT-IR(KBr, cm-1): 3445, 3159, 3103, 2363, 1626, 1564,1460, 1190, 1089, 1048, 783,
605, 507.
Trannsmittance(%)
(c)
4000
3500
3000
2500
2000
1500
1000
500
Wavenumber(cm-1)
Figure S6 (c)FT-IR spectra of Cr(Salen-Cl)-IM- HSO4-MCM-41.
FT-IR(KBr, cm-1): 3441, 3160, 3105, 2361, 1627, 1565,1459, 1191, 1091, 1048, 785,
Weight(%)
607, 509.
(c)
(b)
(a)
100
200
300
400
500
600
700
800
Temperature( C)
o
Figure S7 TG analysis for the Cr(Salen)-IM-Cl-MCM-41(a), Cr(Salen-Cl)-IMHSO4-MCM-41 (b), and Cr(Salen-Br)-IM-HSO4-MCM-41(c).
Figure S8 (a): 1H NMR spectrum of HMF.
1H NMR (D O, 400 MHz): δ 4.68 (s, 2H), 6.66 (d, J = 4 Hz, 1H), 7.51 (d, J = 4 Hz,
2
1H), 9.44 (s, 1H).
Figure S8 (b): 13C NMR spectrum of HMF.
13C NMR (CD Cl, 100 Hz): δ(ppm) 56.06, 110.98, 126.86, 151.81, 161.39, 180.47.
3
Table S1 Dehydration of fructose to HMF using different catalysts
Entry
Catalyst
Time(min
)
Temperature(oC
)
Fructose
conversion (%)
HMF Yield (%)
1
2
3
4
IM-HSO4-MCM-41
IM-HSO4-MCM-41
IM-Cl-MCM-41
IM-Cl-MCM-41
60
60
60
60
130
140
130
140
99.9
99.9
99.9
99.9
87.5
82.3
76.5
74.2
Reaction Conditions: Fructose (100mg), catalyst (40 mg), solvent (2mL DMSO).